Abstract

We present a coarse-grained lattice model of solvation thermodynamics and the hydrophobic effect that implements the ideas of Lum–Chandler–Weeks theory [J. Phys. Chem. B134, 4570 (1999)] and improves upon previous lattice models based on it. Through comparison with molecular simulation, we show that our model captures the length-scale and curvature dependence of solvation free energies with near-quantitative accuracy and 2–3 orders of magnitude less computational effort, and further, correctly describes the large but rare solvent fluctuations that are involved in dewetting, vapor tube formation, and hydrophobic assembly. Our model is intermediate in detail and complexity between implicit-solvent models and explicit-water simulations.

Received 27 October 2010Accepted 09 December 2010Published online 16 February 2011

Acknowledgments:

NIH Grant No. R01-GM078102-04 supported P.V. in the later stages of this work, A.P. throughout, and D.C. in the early stages. In the early stages, P.V. was supported by a Berkeley Fellowship. In the later stages, D.C. was supported by the Director, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division and Chemical Sciences, Geosciences, and Biosciences Division of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. John Chodera and Michael Shirts helped in understanding and implementing MBAR. We thank David Limmer, Ulf Pedersen, and Thomas Speck for a critical reading of the manuscript. We also thank two anonymous reviewers for bringing Refs. 79 and 80 to our attention.